Blue coloring-matters containing sulfur.



UNITED STATES PATENT OFFICE.

ARTHUR LOTTRINGHAUS, HEINRICH you DIESBACH, AND ERNST SCI-IVJARZ, OF. MANN- HEIM, GERMANY, ASSIGNOBS T0 BADISCHE ANILIN & SODA FABRIK, OF LUDWLGS- HAFEN-ON-THE-RHINE, GERMANY, A CORPORATION.

BLUE COLORING-MATTERS CON'IATNING SULFUR.

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No Drawing.

many, have invented new and useful ltns Coloring-Matters Con-- taining Sulfur, of which the following 15 a provements in Blue specification.

()ur invention relates to new coloring matters containing sulfur which are characterized by consisting, when dry, of dark )owders which yield from blue to violet solutions in concentrated sulfuric acid, and which are practically insoluble in caustic alkali solution andin sodium sulfid solution, but yield solutions with a'solution of ammonium sulfid containing caustic soda, which solutions, when poured on filter pa per, rapidly oxidize giving blue to violet stains. Further our new coloring matters are soluble in alkaline hydrosulfite solution yieldingyellowish vats, and dye cotton from these vats from green-blue to violet-blue shades of excellent fastness against the action of washing, potting and light, and those produced from dialkyl-amino compounds are also fast against chlorin.-

\Ve can obtain our new coloringmatters by treating certain para-amino-para-hydroxydiphenylamin compounds or analogous bodies, as hereinafter defined, with alkaline polysulfids containing a high proportion of sulfur, for instance corresponding to the constitution Nil- S to Na' S,', while carrying out the reaction for a comparatively long time in alcoholie or aqueous solution.

Among the-compounds which can be used for the production of coloring 'mattersac-.

pounds containing .halogen in the ortho position to the I hydroxyl group. Further monoalkyl or diallryl para-ammo-paraindophenol-thiosulfonic acids, the corre' sponding u'urcaptaus or disu'ltids and the corn-spc-mling compounds in which the thiazin ring has been formed (see the specification of Letters Patent No. (579,199), or a Specification of Letters Patent.

the second a citizen of the Patented Dec. 30, 1913.

Application filed 0mm 16, 1911. Serial No.-654,796.

leuco compound of any of these bodies may be used. In addition to the aforesaid diphenylannn compounds and indophenol com ounds and the like, the coloring matters which are soluble in sodium sulfid solution and which are obtainable by treating the aforesaid diphenylamin and analogous compounds with sulfur and sodium sulfid can also be treated'according to our invent on and give rise to coloring matters prac- /t1cally insoluble in sodium sulfid solution, but capable of dyeing cotton from an alkaline hydrosulfite. vaf. In particular. we a mention the coloring matter obtainable from dimethyl-thionolin as described in the specification of Letters Patent No. 679,199,

dialkyl-amino-para-hydrexy-dliphenylamins (see the specifications 'of Letters Patent No. 693,632 and of British Patent No. 7726/01).

The crude coloring matters obtained as aforesaid can be purified by extraction with hot sodium sulfid solution which removes impurities, but leaves our new coloring matters undissolved.

The following examples will serve to illustrate further the nature of our invention'and how it can be carried into practical effect, but our invention is not confined to these examples. The parts are by weight.

Example 1: introduce 23.2 parts of anhydrous sodium tetrasulfid into parts of alcohol, add 18 parts of sulfur and heat, in a reflux apparatus, until a solution is obtained. Then add 12 parts of the indophenol obtainable from dimethyl-para-- phenylene-diamin and phenol, and possessing a constitution corresponding to the and boil the mixture for from 40 to +8 hours. Then filter off the product and extract it with hot 10% sodium sulfid solution. The coloring matter thus obtained is practically insoluble in sodium sulfid solution, but with alkaline hydrosulfite it yields a light yellow vat which dyes cotton beautiful 'blue shades of excellent fa-stness, in particular against washing. topping, potting, and chlorin.

a solution from 32 Example 2: Prepare parts of ry tallized sodium sulfid, 19.4

/ v n L and'also those obtainable from the various parts of sulfur, and 16 parts of water, and introduce 8 parts of para-dimethyl-aminopara-hydroxy-diphenylamin and boil the whole, while well stirring, for about 60 hours in a reflux apparatus. Then grind the melt with parts of 10% sodium sulfid, boil .up and filter. Extract the residue repeatedly with hot10% sodium sulfid solution and finally wash with boiling water. The coloring matter has ropert'ies similar to those of the product of Example 1.

Examfple 3: Prepare a solution from 23.2 parts 0 anhydrous sodium tetrasulfid, '18 parts of sulfur and 60 parts'of alcohol, and introduce 12 parts of the indophenol ob-' tainable fromdimethylara-phenylenediamin and -ort'.1omo'no-ch or-phenol, and possessing a constitution corresponding to the formula Cl (CH )IN N 4. =0 and boil the whole vigorously a reflux apparatus for about 40 hours, while. well stirring. Work up the roduct as described in the foregoing examp es, whereupon a colorphenolo the corresponding para-dimethyl amino-pi '-hydroxy-met-meta-dichlor diphenylamin be employed, a coloring matter is obtained which can also be used for dyeing from an alkaline h drosulfite vat yield ing beautifulblue sha es of excellent fastnm Example 4; Heat together, inareflux apparatus, 23.2 parts of anhydrous sodium tetrasulfid,-60,parts of alcohol. and 18 parts of sulfur, and, when solution has taken place, add 12- parts of dimethyl-thiono i i possessing a constitution corresponding to the,

formula 1 lain W; I o

and boil the whole for about 40 hours. Then filter oil the product and extract it with hot 10% sodium sulfid solution. The-coloring matter thus obtained yields a 1i ht yellow vat with alkaline hydrosulfite and dyes cotton beautiful blue shades which are characterized by being much faster, in particular against washing,otojp mg and potting, than the coloringmatterso tainable from methylens violet acco'rdin" to the process of the said'Letters Patent o. 679,199.

Example '5 Prepare-a, solution from -(obtainable'by oxidizing together dimethylpara-phenylene-diamin-thiosulfonic acid and ortho-ortho-dichlor-phenol 1 and reducing the product with sodium sulfid). Boil the:

whole for from 20 to 30 hours, in a reflux v apparatus, and work up the product as described in' the foregoing Example 4. The coloring matter yields a light 'ellow vat with alkaline hydrosulfite and dyes cotton greenish blue shades of excellent fastness.

Example 6: Dissolve 12- parts of paradimethyl-amino-para hydroxy-meta metadichlor-diphenylamin-merca tan in a hot solution of 48 parts of crystallized sodium sulficl in 24 parts of water. Then add 29 parts of 'sulfur and boil the whole, in a reflux apparatus, for about 30 hours. When the mixture'is cold, separate-the reaction product from the supernatant liquid, ind it well, extract it with boiling 10% sodium sulfid solution, and wash it'with water. The coloring matter then has properties similar to those of the coloringmatter obtained according to the. foregoing Example 5.

4 Jxample 7: Introduce 12 parts of the colorin matter obtainable from dimethylthionolm according to the specification of Patent No. 679,199 into a solution of 48 parts of crystallized sodium sulfid in424 rts of water, and then add 29.1 parts 0 sulfur. Boil the whole, in a reflux apparatus, for

from to hours, while stirring, then add 30 parts of 10% sodium sulfid solution, grind the whole, boil up and filter, extract the residue repeatedly with hot 10% sodium sulfid solution and washyit with hot water. The

colorin matter thus-obtained is practically insolublein sodium sulfid solution, butyields a yellow solution in sodium hydrosulfite and alkali, and dyes cotton greenish blue shades of excellent fastness against the action of washing, topping, pottin chlorin and light.

Example 8: Mix toget er,18 parts of sulfur and 60 parts of alcohol and then, while stirring well, add 23.2 parts of anhydrous sodium tetrasulfid. To this solution add 12 arts ofthecoloring'matter obtainable from imethyl-thionolin as described in the s ecification 'of-Patent No. 679,199 and "boi the mixture (while stirring well) for from 80 to 85 hours. Then filter off the coloring matter, extract it repeatedly with hot 10% sodium sulfidsolution, and wash it. It has properties similar to those of the coloring matter obtained according to Example 7 above.

On heating the coloringmatter obtainable from para dimethyl amino para hydroxy-diplienylainin according to the specification of Patent No. 693,632 in a manner analogous to that described in the foregoing Example 8, a coloring matter of similar shade and excellent fastness can be obtained.

Example 9: Heat together, in a reflux apparatus. 23.2 parts of anhydrous sodium tetrasulfid, (30 parts of alcohol and 18 parts of sulfur, and, after solution has been obtained, add 12 parts of the leuco indophenol obtainable by oxidizing together ortlio-chlorphenol and para-phenylene diamin and'reducing the product with sodium sulfid and possessing a constitution corresponding to the formula Then boil the whole, in a-reflux apparatus, for from 80 to 100 hours. Filter oil the coloring matter, extract it with hot 10% sodium sulfid solution and wash it with water. It dyes cotton from a hydrosulfite vat blue shades of excellent fastness against the action of washing and light.

Example 10: Prepare a solution from 23.2 parts of anhydrous sodium -tetrasulfid, 18 parts of sulfur.and parts of alcohol, and add, gradually, 12 parts of the leuco indophenol obtainable from ortho-ortho-dichlor' para-anninophenol and para -xylidcne and possessing a constitution corresponding to the formula CH: Cl

Pioil the whole, in a reflux apparatusffor from T0 to hours and work u the pr0duct as described in the foregoing xainple 9. The coloring matter yields a light cllowsolution in alkaline hydrosulfite an dyes cotton deep violet-blue shades. It has great 'overiiig power and is fast against the action of washing, and light.

Example 11: Treat the leuco indophenol obtained from para-aininophcnol and mono- Copleu ol thh patent may be obtained or five cents each, by addressing the "Commissioner of Patents ethyl-anilin and possessing a constitution corresponding to the formula in the manner described in the foregoing Example 9. The coloring matter thus obtained dyes cotton clear reddish blue shades.

Now what we claim is 1. The new coloring matters containing .sulfur which'consist,-when dry, of dark powders which are soluble in concentrated sulfur c acid giving blue to violet solutions, which coloring matters are practically insoluble in caustic alkali solution and in sodium sulfid solution, but yield solutions with a solution of ammonium sulfid containing caustic soda, which solutions, when poured on filter paper, rapidly oxidize, giving blue to violet stains, which coloring matters also are soluble in alkaline hydrosulfite solution yielding yellowish vats which dye cottoh from green-blue to violet-blue shades of excellent fastness.

2. The coloring matter containing sulfur which is obtainable from dimethyl-thionolin of the formula which coloring matter consists, when dry, of a dark powder which yields a blue solution in concentrated sulfuric acid, which coloring matter is practically insoluble in caustic alkali solution and in sodium sulfid solution,

but yields a solution with aqueous ammonium sulfid containing caustic soda, which solution, when poured on filter paper, ra'pidly oxidizes, giving rise to a bluish-violet stain, which coloring matter yields a li ht yellow vat with alkaline hydrosulfite an dyes cot ton beautiful blue shades of excellent fastness.

In testimony whereof we have hereunto set our hands in thepresence of two subscribing witnesses.

A RJl [UR LU TTRIN GH A U S. TlElN RICH vox DIESBACIT. ERNST SCIIVVARZ. \Vitucsses J; ALEc. Lnovn, Josnrn PFEIFFER.

Washington, D. C." 

